Toner

Specific implementation

, Preferred embodiments of the present invention will be described. In addition, the toner is an aggregate (e.g. powder) of toner particles. The external additive is an aggregate (e.g. powder) of external additive particles. The evaluation results (representing shapes, physical properties, etc.) of the powder (more specifically, the powder of the toner particles, etc.), if not specified, select a large amount of particles from the powder, and measure each of these particles, that is, the result.

D is not particularly limited, and the volume median diameter (D) of the powder is not particularly limited.₅₀ The measured value of the powder has a mean particle diameter measured using a laser diffraction/scattering particle size distribution measuring device ("LA - 950" manufactured by Horiba Horiba Ltd.), and the number average primary particle diameter (average primary particle diameter: area) of 100 primary particles measured by a scanning electron microscope is an average of the diameter) of the circle with the same projected area as primary particle.). The particle diameter (average primary particle diameter).) is measured by a scanning electron microscope.

Unless otherwise specified, the band is electrically indicative of triboelectric chargeability. The positively charged strength (or the negatively charged strength) of the triboelectrification can be confirmed by a well-known charging sequence or the like. For example, for the toner, a standard carrier (negative charge polarity toner for negative charge polarity toner: N - 01; positive charge polarity toner using a standard carrier: P - 01) for toner is charged. Before and after the triboelectric charging, the charged amount of the measurement object is measured using a small-sized MODEL 212 HS charged-quantity measuring device (TREREK, manufactured " by TREK company), respectively, and the charged amount of the charged amount before and after the triboelectric charging becomes stronger as the charging amount of the measurement object is large.

Unless otherwise specified, the measured value Tm) of the softening point (Tm) was a value measured by using a high-flow tester ("CFT-500 D" manufactured by Shimadzu, manufactured by Shimadzu, Ltd.), for. S curves (horizontal axis: temperature; vertical axis: stroke) measured using a high flow tester, the temperature at which stroke is "(baseline stroke value + maximum stroke value)/2" corresponds to Tm (softening point). Unless otherwise specified, the measured value of the melting point (Mp) is a heat absorption curve measured using a differential scanning calorimeter ("DSC - 220") (vertical axis: heat flux (DSC signal); and a horizontal axis: temperature) of the maximum endothermic peak in the temperature). The endothermic peak is due to the melting of the crystallized site. Unless otherwise specified, a measured value of glass transition temperature (Tg) is a value measured by a differential scanning calorimeter ("DSC - 220") measured by "JIS (Japanese Standard) K7121 - 2012" by a differential scanning calorimeter (manufactured by a precision instrument). The heat absorption curve (vertical axis: heat flow (DSC signal); horizontal axis: temperature) measured by differential scanning calorimeter (temperature) of the inflection point (specifically, the extrapolated line of the baseline and the extrapolated line of the falling line) corresponds to Tg (glass transition temperature) in temperature).

Unless otherwise specified, "main component" of a material means a component.

The number average molecular weight (Mn) and the weight average molecular weight (Mw) of each of the measured values of the number average molecular weight (Mn) and the weight average molecular weight (Mw) are values measured using gel permeation chromatography, unless otherwise specified.

The circularity (=the circumference/particle circumference of the circle equivalent to the projection area of the particle) is measured, and the number of measured values is averaged with a flow-type particle image analysis apparatus (manufactured "FPIA (registered trademark) -3000"), for a substantial number (e.g. 3000) of particles.

Unless otherwise specified, the measured value of the interface potential (Zeta eta potential) is a value measured by means of 25 °C a laser Doppler electrophoresis in an aqueous medium pH adjusted to 4 ˜unitunitz-type. In the case where the measurement object is positively charged, the measured value of the interface potential is a positive value. In addition, in the case where the measurement object is negatively charged, the measured value of the interface potential is a negative value.

In the following, "class" is sometimes added after the name of the compound to collectively refer to the compound and its derivatives. In the case where "class" is added after the compound name to represent the polymer name, recurring units that represent the polymer are derived from the compound or a derivative thereof. , Acryl and methacryl are sometimes referred to as "(meth) acryl", and acrylic acid and methacrylic acid are sometimes collectively referred to as "(meth) acrylic". The acrylonitrile and methacrylonitrile are sometimes collectively referred to as "(meth) acrylonitrile".

AOMARKENCODEGTX0AO_POMARKENCODEGTX0AOA

The toner according to the present embodiment can be preferably used for developing an electrostatic latent image, for example. The toner according to the present embodiment may be used as a one-component developer. In addition, a mixing device (for example, a ball mill) may be used to mix the toner with the carrier to prepare a two-component developer.

The toner particles contained in the toner according to the present embodiment have a core, a shell layer and an external additive, wherein the core contains first thermoplastic resin as a binder resin, and the shell layer partially covers the surface, and the external additive is attached to the surface of the core without being covered by the shell layers. The external additive includes external additive particles. The external additive particles protrude further radially outward. At least part of the surface of the external additive particles is exposed from the shell layer. The shell layer comprises second thermoplastic resin or thermosetting resin, and the softening point of second thermoplastic resin is higher than the softening point. The thickness of the shell layer is equal unitunitless 5 nm or more. The method for measuring the thickness of the shell layer is the same method as in the later-described embodiment or similar method thereto. If desired, the core may also contain internal additives (e.g. colorant, release agent, charge control agent, and at least 1 of the magnetic powder).

The toner according to the present embodiment has the above-described structure, and can improve heat resistance and thermal stress resistance. The reason is presumed as follows.

In the toner particles contained in the toner according to the present embodiment, the external additive particles are not covered by the shell layer in the surface of the core, and the core contains first thermoplastic resin. In addition, the shell layer contains second thermoplastic resin or thermosetting resin, and the second thermoplastic resin has a softening point higher than the softening point. That is, in the toner particles contained in the toner according to the present embodiment, the shell layer having a higher surface hardness is exposed to the surface, and the external additive particles are attached to a core having a lower surface hardness. Thereby, the external additive particles can be inhibited from being detached from the core, and the aggregation, therefore, the toner particles can be inhibited, and therefore, the toner according to the present embodiment can be considered to improve the heat storage resistance.

Further, in the toner particles contained in the toner according to the present embodiment, at least a part of the surface of the external additive particles is exposed from the shell layer. In addition, the external additive particles protrude further radially outward. Further, the thickness of the shell layer is unitunitunitless or 5 nm more. SThus, when a thermal pressure is applied to the toner, the cores of the toner particles can be inhibited from contacting each other, and therefore, it is considered that the toner according to the present embodiment can improve the thermal stress resistance property.

In the surface of the core of the toner particles, the area ratio (hereinafter, sometimes referred to as a coverage rate of the external additive) of the 20% area covered by the external additive is preferably equal unitunitless to or equal to the 30% or lower unit_@. By making the coverage of the external additive unitless 20% 30% and less, the external additive particles can be inhibited from being detached from the core, and the aggregation, thereby further improving the heat-resistant storage property. The method for measuring the coverage of the external additive is the same as or similar to the method described in the Examples to be described later on.

, The toner according to the present embodiment will be described in detail with reference to the accompanying drawings.

Structure] of [toner particles]

With reference to 1 and 2, the structure of toner particles contained in the toner according to the present embodiment will be described. Is a view of a cross-sectional structure of toner particles contained in the toner according to the present embodiment. 12 Is a partially enlarged view of a surface layer of the toner particles shown 1 in FIG.

As illustrated 1, toner particles 1 have a core 11, a shell layer 12 and an external additive, and the core 11 contains first thermoplastic resin as a binder resin, the shell layer 12 partially covers the surface, and the external additive is attached to the surface of the core 11 without being covered by the shell layer 11 12 in place. The external additive comprises external additive particles 13. The shell layer 12 contains second thermoplastic resin or thermosetting resin, and the second thermoplastic resin has a softening point higher than that of the core 11. The thickness of the shell layer 12 is unitunitunitally or 5 nm more.

The external additive may cover both the entire surface of the core 11 not covered by the shell layer 12, or may partially cover the position where the shell layer 12 is not covered. However, in order to further improve heat resistance and thermal stress resistance, it is preferable that the outer additive covers the entire surface of the core 11 not covered by the shell layer 12 entirely.

As shown 2 shows, at least a part of the surface of the external additive particle 13 is exposed from the shell layer 12. In addition, the external additive particles 13 protrude from the surface 12A of the shell layer 12 outside the radial Dr of the core 11. To further improve the thermal stress resistance, the protruding height H of the external additive particles 13 is preferably unitunitunitless 30 nm or more. In addition, in order to prevent the external additive particles 13 from being detached from the core 11, aggregation, the protruding height H of the external additive particles 1 is 200 nm preferably unitless @ or less to suppress aggregation of the toner particles 13. The protruding height H of the external additive particles 13 may be adjusted by changing at least one of the thickness of the shell layer 12 and the particle size of the external additive particles 13. , In FIG. 2, the external additive particles 13 are attached in a state of being embedded in the core 11, but the external additive particles 13 may not be attached in a state of being embedded in the core 11 or not in a state of being embedded therein. However, in order to improve adhesion between the external additive particles 13 and the core 11, the external additive particles 13 are preferably attached so as to be embedded in the core 11 to adhere. , In FIG. 2, the surface 12A of the shell layer 12 is a straight line, and in the actual toner particles, the surface of the shell layer is spherical in shape.

The case layer 12 may be substantially made of a thermosetting resin, or may be substantially composed of second thermoplastic resin, or may contain both a thermosetting resin and second thermoplastic resin. Further, the structural material of the shell layer 12 may use a material in which an additive (e.g. a charge control agent) is added to the resin. In order to further improve the thermal stress resistance and the heat resistance storage property, the content of the shell layer 12 in the structural material, the thermosetting resin and second thermoplastic resin is preferably 80 mass % or more, more preferably 90 mass % or more, and particularly preferably 100 mass %.

When the shell layer 12 contains second thermoplastic resin, the softening point second of the thermoplastic resin is preferably equal to or more than the softening point of the core 11 in order to further improve the heat-resistant storage property and the thermal stress 25 °C resistance. , When the shell layer 12 contains second thermoplastic resin, in order to improve the low-temperature fixability, the softening point second of the thermoplastic resin is preferably equal to or less than +35 °C that of the core 11 in order to improve the low-temperature fixability of the toner.

When the shell layer 12 contains second thermoplastic resin, in order to further improve the heat resistance and thermal stress resistance, the shell layer 12 has a thickness that is more or 40 nm higher. , When the shell layer 12 contains second thermoplastic resin, in order to improve the low-temperature fixability of the toner, the shell layer 12 has a thickness that is less than or equal to 'unitz 50 nm'.

When the shell layer 12 contains a thermosetting resin, in order to improve the low-temperature fixability of the toner, the shell layer 12 has a thickness that is less than or equal to 6 nm unitz @.

In order to further improve heat resistance and thermal stress resistance, the number average primary particle diameter of the external additive particles 13 is preferably unitless or 100 nm more. , In order to prevent the external additive particles 13 from being detached from the core 11, aggregation, particle 1 of the external additive particles 13, and the like are inhibited from agglomerating, and the primary particle diameter of the external additive particles D is preferable to be below unitz 200 nm or lower.

In order to obtain toner suitable for image formation, the volume of toner particles 1 is smaller in size (D).₅₀ Each unitz type is preferably unitunitunitless or less 4 μm.) unitunitally 9 μm or less unitunitally.

The shell layer 12 and the external additive preferably have a polarity opposite to that of the core 11 with respect to the charging polarity. When the structure of the shell layer 12 and the external additive is the opposite to the charging polarity of the core 11, the toner according to the present embodiment can be easily produced by the manufacturing method A described later, for example, in the present embodiment. For example, when the shell layer 12 and the external additive are positively charged and the core 11 is negatively charged (hereinafter, sometimes referred to as a positively chargeable toner structure), a positively chargeable toner can be easily produced by the manufacturing method A (described later) as the toner according to the present embodiment.

In order to make the charging polarity of the shell layer 12 and the external additive be opposite to that of the core 11, the shell layer 12 and the external additive are preferably made of a material different from that of the core 11. To obtain a toner having a positively chargeable toner structure, it is preferable that the shell layer 12 and the external additive-containing structural material use a positively charged material (for example, a material positively charged by friction with the carrier), and, the structural material of the core 11 uses a negatively charged material (e.g. a material negatively charged by friction with the carrier).

The positively chargeable material is, for example, a cationic functional group-containing material. Examples: The cationic functional group includes an amino, a quaternary amine cation, an amide group, and a nitrogen-containing heterocyclic group. The nitrogen-containing heterocyclic group is, for example: pyridine ring group, pyrazine ring group, pyridazine ring group, pyrimidine ring group, and triazine ring group. In addition, the positively chargeable material may also be used as a positively chargeable charge control agent or a combination thereof.

A negatively chargeable material such as a material having an anionic functional group. Examples: Alkyl, hydroxyl, ether, and acidic groups are anionic functional groups. In addition, the negatively chargeable material can also be.

[Element] of toner particles.

Next, elements of the toner particles included in the toner according to the present embodiment will be described. (Binder resin)

A large part (for example, 70 mass % or more) of the binder resin accounts for the components of the core. Thus, it is considered that the properties of the binder resin significantly affect the properties. By combining several kinds of resins to be used as the binder resin, the properties (more specifically, softening point, acid value, etc.) of the binder resin can be adjusted. In addition, by changing the softening point, the softening point.

The core contains first thermoplastic resin as the binder resin. The first Thermoplastic resins are, for example: styrene resins, acrylate resins (more specifically, acrylate polymers, methacrylate polymers, etc.), olefin resins (more specifically, polyvinyl resins, polyvinyl alcohol, vinyl ether resins, N - vinyl resins, etc.), polyester resins, polyamide resins, and polyurethane resins. , The copolymer, that is, a copolymer (more specifically, a styrene - acrylate-based resin, a styrene - butadiene-based resin, etc.) into which any repeating unit is introduced in the resin may also be used as first thermoplastic resin.

The first Thermoplastic Resins are obtained by addition polymerization, copolymerization or polycondensation of more than one thermoplastic monomer (s). Further, the thermoplastic monomer is a monomer (more specifically, an acrylate-based monomer, a styrene-based monomer, etc.) which is a thermoplastic resin by homopolymerization, or a monomer (e.g. a combination) of a monomer that becomes a thermoplastic resin by polycondensation (for example, a polyol and a polyvalent carboxylic acid obtained by polycondensation.

To obtain a toner having a positively chargeable toner structure, first thermoplastic resin is preferably a polyester resin.

The polyester resin is obtained by polycondensing one or more polyhydric alcohols with more than one polycarboxylic acid. The alcohol used for synthesizing the polyester resin is, for example, a diol (more specifically, a diol type, a bisphenol, etc.) as shown below, and an alcohol having a trivalent or higher alcohol. The carboxylic acid used for the synthesis of the polyester resin is, for example, a dicarboxylic acid or more than three carboxylic acids as shown below. Further, a polycarboxylic acid derivative capable of forming an ester bond by polycondensation of an acid anhydride, a polyvalent carboxylic acid halide or the like of a polycarboxylic acid may be used instead of the polycarboxylic acid.

For example: ethylene glycol, diethylene glycol, triethylene glycol, 1, 2 - propylene glycol, 1, 3 - propylene glycol, 1, 4 - butanediol, 2 -1 butylene 4 - 1 pentene 5 - 2 - 6 - 4 - 1 -1 cyclohexane dimethanol, dipropylene glycol, 1 5 - 1 benzene glycol, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol 4 .

The bisphenol A, for example: bisphenol A, hydrogenated bisphenol A, bisphenol A ethylene oxide adducts and bisphenol A propylene oxide adducts.

For example: sorbitol, 1, 2, 3, 6 - hexanediol, 1, 4 - sorbitan, pentaerythritol, dipentaerythritol, tripentaerythritol, 1, 2, 4 - methylglycerol, 1 methyl 2, 5 - 2 - 4 - butanetriol, trimethylolethane, trimethylol propane and 1 2 - 3, 5 -1, 2 trihydroxytoluene.

Examples of dicarboxylic acids are, for example: maleic acid, fumaric acid, citraconic acid, malonic acid, adipic acid, phthalic acid, isophthalic acid, sebacic acid, azelaic acid, isododecanedioic acid, n-dodecenylsuccinic acid, n-octenyl succinic acid, n-dodecenylsuccinic acid, isododecenylsuccinic acid, and the like), and alkenylsuccinic acid (more specifically, n-butyl succinic acid, n-octylsuccinic acid, n-dodecenylsuccinic acid, and the like), and succinic acid, maleic acid, succinic acid, succinic acid and alkyl succinic acid.

For example: 1, 2, 4 - benzoic acid (trimellitic acid), 2, 5, 7 - naphthoic acid, 1, 2, 4 -hexanetricarboxylic acid, 1, 2, 4 - cyclohexanetricarboxylic acid, tetrakis (methylene carboxy) methane, 1, 2 3 -2 - 5 - 8 -2 - 1 octane tetracarboxylic, pyromellitic acid, and Empmpol trimeric acid are preferred for the purposes of the present 1 invention 2, 4 - and are not limited to these types of acid salts 1 2 7.

(Colorant)

The core may also contain a colorant. The colorant may be used in combination with the color of the toner to use a known pigment or dye. In order to form a high-quality image using toner, the amount of the colorant is preferably 100 parts by mass to 1 parts by mass with respect to 20 parts by mass of the binder resin, or less.

The core may also contain a black colorant. Black colorants such as carbon black. In addition, the black colorant may be a colorant that is toning black using a yellow colorant, a magenta colorant, and a cyan colorant.

The core may also contain a colored colorant. Examples: The yellow colorant, the magenta colorant, and the cyan colorant.

Examples of the yellow colorant include a condensed azo compound, an isoindolinone compound, an anthraquinone compound, an azo metal complex, a methine compound, and an aromatic amide compound. The yellow colorant is, for example: C.I. Pigment Yellow (, and), naphthol yellow S, Hansamba G and and C.I. vat yellow. 194 3 12 13 14 15 17 62 74 83 93 94 95 97,109,110,111,120,127,128,129,147, 151,154,155,168,174,175,176,180,181, 191

Examples of the magenta colorant include a condensed azo compound, a pyrrolopyrrole dione compound, an anthraquinone compound, a quinacridone compound, a basic dye lake compound, a naphthol compound, a benzimidazole ketone compound, a thioester compound, and a perylene compound. Magenta colorant, for example: C.I. Pigment Red (, and). 1 57 1,122,144,146,150,166,169,177,184, 185,202,206,220,221 81 2 3 254 5 6 7 19 23 48 2 48 3 48 4

Examples of the cyan colorant include one or more compounds selected from the group consisting of copper phthalocyanine compounds, anthraquinone compounds, and basic dye lake compounds. Cyan colorants For example: C.I. Pigment Blue (1, 7, 15, 15: 1, 15:2, 15:3, 15: 4, 60, 62 and 66), phthalocyanine blue, C.I. vat blue and C.I. Acid Blue.

(Mold release agent)

The core may also contain a release agent. The release agent may be used, for example, to improve high temperature resistance of the toner. To improve the high temperature resistance of the toner, the amount of the release agent is preferably 100 parts by mass or more 1 parts by mass or less with respect to 20 parts by mass of the binder resin.

Examples of waxes of aliphatic hydrocarbon waxes such as low molecular weight polyethylene, low molecular weight polypropylene, polyolefin copolymer, polyolefin wax, microcrystalline wax, paraffin, Fischer-Tropsch wax, fatty acid ester wax, petrolatum wax, and fatty acid ester wax; and wax (for example, carnauba wax) after fatty acid ester deoxidation are partially or completely oxidized; wax, wax, carnauba wax, petrolatum and the like can be used as a mold release agent such as polyethylene wax, paraffin wax, and fatty hydrocarbon wax such as polyethylene wax, paraffin wax, and rice bran wax; and other waxes such as paraffin wax and polyethylene wax can be used as a mold release agent such as polyethylene wax, carnauba wax, and petrolatum wax. In the present embodiment, a release agent, or a plurality of release agents, may be used alone or in combination.

(Charge control agent)

The charge control agent may be used, for example, to improve charge stability or charge-up characteristics of the toner. The charge-up characteristic of the toner is an index. However, in the case where the toner has sufficient electrification property, it is not necessary to make the toner core contain a charge control agent.

When the core contains a negatively chargeable charge control agent, it is possible to enhance the anionic. In addition, by containing the positively chargeable charge control agent, it is possible to enhance the cationic.

Acid dyes such as pyridazine, pyrimidine, pyrazine, oxazine, benzothiadiazine, and oxadiazine, and, and (methylacryloyloxy) ethyltrimethyl ammonium chloride, aminopropylacrylamide chloromethyl quaternary salt and the like are exemplified, for example: pyridazine .triazine, and oxazine, and, optionally, preferably or benzothiadiazine, and, benzothiadiazine . or, and other quaternary ammonium salts such as phenazine, and triazine . FIGS. and, and pharmaceutically acceptable salts thereof are shown in the following general formula (b, S. Pat; and wherein n is or halogenolazine GR, or a pharmaceutically acceptable salt thereof, such as azinium, pyridine, pyrazine, methoxy, or . and pharmaceutically acceptable salts of these organic carboxylic acids are described in. S. Chem. Asserv. Chem. EW, which is a compound; and is a pharmaceutically acceptable salt or solvate of n-methyl ammonium chloride, benzothiazine, pyrazine, oxazine, and benzodiazoxide, and pharmaceutically acceptable salts of these organic carboxylic acids are shown in FIGS.), and, and pharmaceutically acceptable salts of these organic carboxylic acids are mentioned in. S. Pat. 4 6 - 1 3 5 - 1 2 1 2 - 1 3 - 3 1 4 4 - 1 5 - 2 - 12 BK 1 1 3 - 4 - 2 1 BH/C 1 3 - 4 - 2 3G 1 5 - 3 4 - 1 2 3 4 - 1 3 RL 2 6 - 1 1 3 2 - 5 - 3 1 4 - 3 2 1 4 2 1 4 - 2 1 5 .

The negatively chargeable charge control agent is, for example: an organometallic complex as a chelate compound. The organometallic complex is preferably: an acetylacetone metal complex, a salicylic acid-based metal complex, or a salt thereof.

In the present embodiment, it is possible to use only one charge control agent, but it is also possible to use. In order to improve the charging stability, the content of the charge control agent is preferably 100 parts by mass or more 0.1 parts by mass or less relative to 10 parts by mass of the binder resin.

(Magnetic powder)

The core may also contain magnetic powder. Examples: a ferromagnetic metal (more specifically, iron, cobalt, nickel, etc.) and an alloy, a ferromagnetic metal oxide (more specifically, ferrite, magnetite, chromium dioxide, etc.) and a material subjected to the ferromagnetic treatment (more specifically, a ferromagnetic carbon material by heat treatment, etc.). In the present embodiment, a magnetic powder, or a plurality of magnetic powders, may be used alone or in combination.

(Shell)

The shell layer includes at least one of a thermosetting resin and second thermoplastic resin. The second The thermoplastic resin may, for example, be a thermoplastic resin exemplified by first thermoplastic resin contained in the core, as long as it is a thermoplastic resin having a softening point higher than the softening point of the core and is not particularly limited, for example.

In the case where the shell layer contains a thermosetting resin, a toner having a positively chargeable toner structure, preferably one or more, more preferably melamine resin, is selected from the group consisting of urea resin, melamine resin, and styrene-generation melamine resin, preferably melamine resin.

In the case where the shell layer contains second thermoplastic resin, the toner, second thermoplastic resin, which is a positively chargeable toner structure is obtained, which is preferably a thermoplastic resin containing a quaternary amine cation-based resin.

Thermoplastic resins comprising quaternary amine cationic groups are, for example: polymers containing quaternary amine cation-based vinyl compounds, and copolymers of vinyl compounds comprising quaternary amine cationic groups with other vinyl compounds. Further, the vinyl compound is vinyl (CH).₂ (=CH CH-) or a compound having a hydrogen substituted with hydrogen in a vinyl group (more specifically, ethylene, propylene, butadiene, ethylene, (meth) acrylic, methyl (meth) acrylate, (meth) acrylonitrile, styrene, and the like). When the vinyl compound, a carbon-carbon double bond (C=C) contained in the vinyl group or the like is subjected to addition polymerization, a polymer (resin) is obtained.

Vinyl compounds comprising quaternary amine cationic groups are, for example: vinylbenzyl trialkylammonium salts, 2 - (acryloyloxy) ethyl trialkylammonium salts and 2 - (methacryloyloxy) ethyl trialkylammonium salts. Further, the quaternary amine-containing vinyl compound may be a compound in which a quaternary amine containing a tertiary amine group such as methyl methacrylate 2 - (diethylamino) ethyl or the like is quaternized.

Vinyl benzyl trialkyl ammonium salts such as: vinylbenzyl trimethyl ammonium salts (more specifically vinylbenzyl trimethyl ammonium chloride, etc.), vinylbenzyl dimethyl ethyl ammonium salts (more specifically vinylbenzyl dimethyl ethyl ammonium chloride, etc.) and vinylbenzyl dimethyl pentyl ammonium salts (more specifically vinylbenzyldimethylammonium chloride, etc.). alpha.vinylbenzyl dimethyl ammonium salt (more specifically vinylbenzyl dimethyl ammonium chloride and the like) and vinylbenzyl dimethyl ethyl ammonium salt (more specifically vinylbenzyl dimethyl ammonium chloride)), vinyl benzyl dimethyl ethyl ammonium chloride, and the like are, for example, vinyl benzyl dimethyl ethyl ammonium chloride, and the like).

2 - (Acryloxy) ethyl trialkylammonium salt, for example: 2 - (acryloyloxy) ethyl trimethyl ammonium chloride, etc.), 2 - (acryloyloxy) ethyltrimethyl ammonium chloride, etc.) and 2 - (acryloyloxy) ethyl dimethyl n-pentyl ammonium salt (more specifically, 2 - (acryloyloxy) ethyl dimethyl n-pentyl ammonium chloride and the like). and the like are obtained. (More specifically, 2 2 - (acrylamido) ethyltrimethyl ammonium 2 - chloride, and the like) 2 .

2 - (Methacryloyloxy) ethyl trialkylammonium salt, for example: 2 - (methacryloyloxy) ethyltrimethyl ammonium chloride, etc.), 2 - (methacryloyloxy) ethyldimethyl ethyl ammonium chloride and the like) and 2 - (methacryloyloxy) ethyldimethyl n-pentyl ammonium salt (more specifically, 2 2 - (methacryloyloxy) ethyldimethyl n-pentyl ammonium chloride and the like) 2 .

Other vinyl compounds copolymerizable with vinyl compounds containing quaternary amine cationic groups include, for example: styrene, o-methylstyrene, p-octylstyrene, n-octyl styrene, n-hexyl styrene, n-octyl styrene, n-octyl styrene, n-octyl styrene, n-dodecyl styrene, n-octyl styrene, n-octyl styrene, n-octylstyrene, n-octyl styrene, n-dodecyl styrene, and n-octylstyrene. (trifluoromethyl) acrylate, methyl) ethyl acrylate, (meth) acrylic acid ethyl acrylate, n-octylstyrene, n-octyl styrene, n-octylstyrene and the like; (meth) acrylic; (meth) acrylonitrile. 2 4 . The vinyl compound containing a quaternary amine cation group may be copolymerized with one of the other vinyl compounds described above, or may be copolymerized with two or more of the other vinyl compounds described above in combination.

(External additive)

The external additive particles contained in the external additive are preferably inorganic particles, more preferably silica particles and metal oxides (more specifically, aluminum oxide, titanium oxide, magnesium oxide, zinc oxide, strontium titanate, barium titanate, and the like) particles. In the present embodiment, one kind of external additive particles, or several kinds of external additive particles, may be used alone or in combination.

The external additive particles may be surface-treated. For example, in the case where the external additive particles use silica particles, the surface of the silica particles may be made hydrophobic and/or negatively charged by the surface treatment agent. For example: a coupling agent (more specifically, a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, etc.), a silazane compound (more specifically, a chained silazane compound, a cyclic silazane compound, and the like) and a silicone oil (more specifically, dimethyl silicone oil and the like). The surface treatment agent is particularly preferably a silane coupling agent and a silazane compound. Examples of the silane coupling agent include silane compounds (more specifically, methyltrimethoxysilane, aminosilanes, and the like). For example HMDS (hexamethyldisilazane). After the surface of the silica substrate (untreated silica particle) is treated by the surface treatment agent, a large amount of hydroxyl (- OH) present on the surface of the silica substrate is partially or entirely substituted with a functional group derived from the surface treatment agent. Thus, a silica particle having a functional group derived from a surface treatment agent (specifically, hydrophobic and/or a functional group having a positive electric property) derived from the surface treatment agent is obtained.

To obtain a toner having a positively chargeable toner structure, the external additive particles are preferably positively chargeable silica particles which are surface-treated with aminosilanes, and positively charged titanium dioxide particles which are surface-treated with aminosilanes. Aminosilanes are, for example: 3 - aminopropyltrimethoxysilane, 3 - aminopropyltriethoxysilane, N - (aminoethyl) -3 - aminopropylmethyldimethoxysilane, N - (aminoethyl) -3 - aminopropyltrimethoxysilane.

In order to improve flowability or handleability, the amount of the external additive is preferably 100 parts by mass to 0.1 parts by mass with respect to 20 parts by mass of the core or less.

(Combination) of materials

, The core contains a polyester resin as a binder resin, and the shell layer contains at least one of a thermoplastic resin containing a quaternary amine cation group and a melamine resin, and the external additive contains at least one of positively chargeable silica particles and a positively chargeable titanium dioxide particle subjected to surface treatment with aminosilane, and a melamine resin containing a quaternary amine cation group, and a melamine resin containing a quaternary amine cation group as the binder resin, and the shell layer contains a melamine resin .

[Method for producing toner]

Next, a preferred manufacturing method (hereinafter, sometimes referred to as manufacturing method A) of the toner according to the present embodiment will be described. The production method A includes a core preparation step (core preparation step), an external additive attaching step (external additive attaching step), and a shell layer forming step (a shell layer forming step). , The production method A may further include a cleaning step, a drying step, and a pulverizing step after the shell layer forming step, for example. , An example of each step of the cleaning step, the drying step, and the pulverization step will be described.

(Nucleus preparation process)

In the core preparation step, the core.

One method of crushing is to first mix the binder resin and the internal additive added as necessary. Next, a melt-kneading device (for example, a uniaxial or biaxial extruder), and the resulting mixture are melt-kneaded. , The obtained melt kneaded product is pulverized and fractionated. Nuclei.

For example, one aggregation method is to aggregate these fine particles into a desired particle diameter first in an aqueous medium containing a binder resin and individual fine particles according to an internal additive to be added as needed, to aggregate the fine particles into a desired particle diameter. Thereby, aggregated particles containing a binder resin and the like are formed. , The obtained agglomerated particles are heated, so that the components contained in the aggregated particles are integrated. Nuclei.

(External additive attaching process)

Then, an external additive is attached to a portion of the surface of the core. In this step, an external additive adhesion core having a core and a core and an external additive attached to a part of the surface of the core is obtained. A method of attaching an external additive to a portion of the surface of the core uses, for example, a mixing apparatus, by mixing the core with the external additive particles, to adhere an external additive particle to a portion of the surface of the core.

Method (shell layer forming process)

Then, a shell layer is formed on the surface of the external additive adhesion core without the external additive attached thereto. For example: an in-situ polymerization method, a liquid-in-liquid film curing method, and a cohesive method are described. More specifically, for example, after the raw material (shell material) for forming the shell layer and the external additive are attached to the aqueous medium, a shell raw material reaction (e.g. thermal curing reaction) is performed on the surface of the external additive adhesion core by heating the aqueous medium, thereby forming a shell layer on the surface of the external additive adhesion core. To the method, the thickness of the shell layer can be adjusted by changing the usage amount of the shell raw material. Further, by forming the shell raw material, the external additive, and the core, the reaction of the shell raw material may be selectively performed on the surface of the external additive adhesion core without the attachment of the external additive by using a material having a different charge polarity. To obtain a toner having a positively chargeable toner structure, it is preferable, that the structure material of the shell raw material and the external additive uses a positively chargeable material and, as a structural material of the core, a negatively chargeable material.

In addition, the shell raw material may be a dispersion. For example, in the case of forming a shell layer having positively chargeable properties, a dispersion (positively chargeable resin particle dispersion) containing resin particles with a positively chargeable material may be used). In addition, in the case of forming a shell layer having a negatively chargeable property, a dispersion (negatively chargeable resin particle dispersion) containing a resin particle with a negative electrical material may be used, for example). More specifically, after an external additive is added to the aqueous medium and a dispersion of the resin particles is added, the surface of the core is attached to the surface of the external additive attaching core (bonding), thereby forming a shell layer on the surface of the external additive adhering core. The aqueous medium is heated, thereby forming a shell layer on the surface of the external additive adhering core . In this method, by changing the amount of the dispersion of the resin particles, the thickness of the shell layer can be adjusted. In addition, the resin particles and the external additive and the core are formed by using a material having a different electric polarity, and the film formation of the resin particles may be selectively performed in a position where the external additive is not attached to the surface of the external additive adhesion core. In order to obtain a toner having a positively chargeable toner structure, it is preferable, that the structure material of the resin particles and the external additive uses a positively chargeable material, and a material constituting the core uses a negatively chargeable material. To further improve the low-temperature fixability and the heat-resistant storage property, the number-average 40 nm primary particle diameter of the resin particles is preferably equal unitunitless to or equal in a range of 'unitz 60 nm' or less.

By the manufacturing method A described above, the toner according to the present embodiment can be easily produced. Further, the method for producing the toner according to the present embodiment is not limited to the above-described manufacturing method A. For example, after the surface of the core is partially covered with the shell layer, the toner according to the present embodiment may be produced by attaching an external additive to the surface of the core that is not covered by the shell layer.

[Example]

Next, an embodiment of the present invention will be described. First, a measurement method of the softening point and the glass transition temperature will be described.

Measurement of AOMARKENCODEGTX0AO_softening point (Tm): AOMARKENCODEGTX0AO_.

A sample (more specifically, a core, a thermoplastic resin, or the like) was filled into a high-flow tester ("CFT-500 D" produced by Shimadzu). Then, under the mold capillary apertures unit_@, the 1 mm plunger is subject to 20 kg/cm.² Within the condition of 6 °C/the intensification of the temperature rise rate unit_@ was used 1 cm.³ The sample was dissolved and discharged, and S-shaped curve (horizontal axis: temperature; vertical axis: stroke) of the sample was obtained. From the resulting S-curve, the softening point of the sample was read. In S-type curves, the maximum stroke is S.₁ Stop value S, at low temperature side, of the base line₂ At the time, the value of the stroke in S-type curve reaches " (S).₁ + S₂ The temperature at the time of/2" is equivalent to the softening point (Tm) of the sample.).

Measurement of glass transition temperature (Tg) of _AOMARKENCODEGTX0AOA

The measurement device uses a differential scanning calorimeter ("DSC - 220" manufactured by Seiko Co. Ltd.). A sample (more specifically, a core, a thermoplastic resin, and 10 mg so) were unitarily @ charged into an aluminum vessel (aluminum container), and the aluminum vessel was mounted to a measurement unit of the measurement apparatus. Further, an empty aluminum vessel was used as the reference object. Then, the temperature of the measurement unit was raised from the -20 °C start of 10 °C/the measurement starting temperature unit_@ 150 °C minute (1st times warm-up: RUNUN1). , The temperature of the measurement unit was 150 °C allowed to 10 °C/be cooled down depending on the velocity of unitz @ minute. 'unitz -20 °C'. , The temperature of the measurement unit was raised again -20 °C from the 10 °C/divided speed up from the 150 °C (2nd times temperature increase: RUNUN2). Through RUNUN2, a heat absorption curve (vertical axis: heat flow (DSC signal); horizontal axis: temperature) of the sample was obtained. Tg of the sample was read from the resulting heat absorption curve. In the heat absorption curve RUNUN2, the temperature (starting temperature) of the inflection point (the intersection of the extrapolated line of the baseline and the extrapolated line of the falling line) caused by the glass transition corresponds to Tg.

AOMARKENCODEGTX0AOA For AOMARKENCODEGTX0AO_nuclear CA

Four flask equipped with thermometer (thermocouple), dehydration tube, nitrogen inlet tube, rectification column and stirring device, and capacity 5L were fitted to the oil bath and 1, 2 - propylene glycol 1200 g, terephthalic acid @datdatdatas, 1700 g stannous octoate 3g were added to the flask. Then, under nitrogen atmosphere, the contents of the 230 °C flask were subjected to a unitz @ (in particular, a condensation 15 hours reaction) under the condition of a constant temperature unit_@. , The flask contents were decompressed, and under reduced pressure atmosphere (pressure 8.0 kPa) and 230 °C under the same temperature, the contents of the flask were reacted, until Tm of the reaction product (polyester resin) reaches a 100 °C predetermined unitz.), the flask contents were evaporated under reduced pressure. Thus, Tg48 °C and Tm100 °C polyester resin.

A FM mixer (NIPIPIPIPX0AO_ENGGGGGGGGINEERING. CO . ltd. "FM - type"), the colorant (C.I. Pigment Blue @timetime@; component: copper phthalocyanine pigment) 100 15:3 parts by mass of NISSSSSSSSSSSSAN ELECTOL (Japan registered 5 trademark) WEP EP EP-3", Melting unitum®) 73 °C was blended (dry-mixed) 2400 rpm at a tachounitic. RTM . Ltd. and a release agent (Japan Registered Trade Mark.) 5 mass parts, respectively.

Next, the resulting mixture was melt-kneaded using a twin-screw extruder ("PCM - 30" manufactured by Kuismaka '). , The obtained kneaded product was cooled. Next, a "turbo mill T250") was manufactured using a mechanical pulverizer (FREREREUND-TURURURURURURURURBO), and the cooled kneaded material was pulverized under the condition of setting 5.6 μm the particle size unitunitunit_@ unitunitz @. Next, "Elbow-Jet EJ-LABABO type") was manufactured using a classifier (manufactured by Japan), and the obtained pulverized material was classified. , A volume median diameter (D) is obtained.₅₀ ) Is a powder of KCA-like nuclear CAs. 6.0 μmWith respect to the resulting core CA, the circularity is 0.931, Tg is 50 °C unitunitunitant @, Tm is unitunitunitant 98 °C, and the interface potential at pH 4 4 - 2020mv.]In addition, the obtained nuclear CA and the standard carrier N - 01 (a standard carrier) for negatively-charged polar toner supplied by Japanese Patent - 2020202020μC/g. The core CA preferably has an anionic (negatively chargeable) depending on the data, in which the interface potential and the triboelectric charge amount are charged.

Preparation of AOMARKENCODEGTX0AOA with positive electrical resin particle dispersion liquid of AOMARKENCODTX0AOA

[Preparation] of positively chargeable resin particle dispersion PA

A flask equipped with a thermometer (thermocouple), nitrogen inlet tube, stirring device, and condenser (heat exchanger), having a capacity 2L, was added with isobutanol 250 g, 2 - (diethylamino) ethyl 6g, and p-toluenesulfonic acid methyl 6g. Then, under a nitrogen atmosphere, the contents of 80 °C the flask were subjected to a residue-like @ (quaternary amine reaction 1 hour) under the presence of a constant temperature. Next, a flask was charged with nitrogen, and n-butyl acrylate 230 g, a polymerization initiator (t-butyl peroxy (2 -ethylhexanoate) tert-butyl peroxide: ARKKKKKKKKet Co. Ltd.) 12g was added to the flask. , The temperature of the inside of the flask was maintained to be unitz 95 °C (polymerization temperature), and the contents of the flask were stirred into the flask® 3 hours. , A polymerization initiator (t-butyl peroxy (2 - ethylcaproic acid) tert-butyl ester: ARKEKEKEKEKEKEKEY manufactured) 12g, which holds the internal temperature of the flask, 95 °C is then added to the flask, and the contents of the flask 3 hours are stirred into the flask®.

Next, the contents of the 140 °C flask were dried to remove isobutanol under the presence of a thermostatic unitz® and pressure 10 kPa. , The contents of the flask were pulverized, to obtain a coarse pulverized product. Next, "turbo mill) T250") was manufactured using a mechanical pulverizer (FREREREUND-TURURURURURURURURBO), and the above coarse pulverized material was further pulverized under the condition of setting 10 μm the particle size unitunitunitarily to obtain a fine powder fragment. Next, the resulting fine powder fragment 100 g, cationic surfactant (manufactured "QUUUUARTAMIN (Japan registered trademark) 24P", aqueous sodium lauryl trimethyl ammonium chloride aqueous solution having a concentration 25 mass %) 2g 0.1 hmol/L was mixed, 25g thereby obtaining a dispersion liquid.

Next, ion exchange water, which was added to the resulting dispersion, was added to prepare a slurry of total. 400 g, The obtained slurry was added to a stainless steel pressure-resistant round bottom container. Next, " clearmix (Japan Registered) CLM M M M M (manufactured by M····Ltd.), was used to shear the above-mentioned slurry for 30 minutes under 140 °C the condition that the 2000 0 rpm rotor rotational speed unitunitunitdly @ under the context of a thermostatic unitant type 0.5 mpa and a pressulinic type.), the slurry is chopped. , A dispersion (positively charged resin particle 5 °C/dispersion PA) containing positively charged resin particles (particles made of 50 °C a thermoplastic resin containing a quaternary 15000 rpm amine cation group) is obtained while keeping the contents of the container unitarily @ minute until the temperature within the container reaches a unitunitz-divided speed until the temperature within the container reaches a unitz-type-like manner, to obtain a solid content concentration 30 mass % of positively charged resin particles (particles containing a quaternary amine cation-based thermoplastic resin).]In the case of positively chargeable resin particles contained in PA-containing positively chargeable resin particle dispersion (PA), the number-average primary 50 nm particle diameter is 59 °C unitunitunitant @, 124 °C Tg is unitunitunitant @, Tm is unitunitunitant @, and pH 4 4 is 21 mV. ANG. Based on the data, the positively chargeable resin particles contained in the positively chargeable resin particle dispersion PA have a cationic (positively chargeable) property, and the cationic (positively chargeable) resin particles are positively charged.

[Preparation] of positively chargeable resin particle dispersion PB

In addition to the addition of n-butyl acrylate 230 g to styrene 155 g and n-butyl acrylate 75g, a dispersion (positively charged resin particle dispersion PB) containing positively charged resin particles (particles composed of a quaternary amine cation-containing thermoplastic resin 30) was obtained in the same manner as the preparation of n-butyl acrylate (PA) in addition to n-butyl acrylate (PA) and n-butyl acrylate (PA) in the preparation method, and the additive amount .% by mass of n-butyl acrylate. The positively chargeable resin particles PB contained in the obtained positively charged resin particle dispersion liquid PB have a unitunitant particle size, Tg is unitunitunitant 50 nm, Tm is unitunitunitant 60 °C, and the 125 °C zeta potential at pH 4 4 is 20 mV. The obtained positively chargeable resin particle dispersion liquid PB has a number average primary particle size of about unitz @ and a Tm of about unitz @. On the basis of the data, the positively chargeable resin particles contained in the positively chargeable resin particle dispersion PB have cationic (positively chargeable) properties, depending on the data of the Zeta potential).

[Preparation] of PC with positively chargeable resin particles

In addition to the addition of n-butyl acrylate 230 g to styrene 120 g and n-butyl acrylate 110 g, a dispersion (a positively chargeable resin particle dispersion PC) containing positively charged resin particles (particles composed of a quaternary amine cation-containing thermoplastic 30 resin) was obtained in the same manner as in the preparation of the positively-conductive resin particle dispersion PA, except that n-butyl acrylate was changed to the styrene resin particle dispersion liquid PA and the addition amount of the n-butyl acrylate copolymer . In addition, when styrene is copolymerized with n-butyl acrylate, Tm tends to be lowered when the proportion (molar ratio) of styrene is reduced, and the resulting copolymer (thermoplastic resin) tends to be lowered. In the case of positively chargeable resin particles contained in PC containing positively chargeable resin particles, the number-average primary particle diameter is unitunitunitant 50 nm, Tg is 40 °C unitunitunitant @, 95 °C Tm is unitunitunitant @, and pH 4 4 is 20 mV. ANG. On the basis of the data, the positively chargeable resin particles contained in PC-charged resin particle dispersion PC have a cationic (positively chargeable) property, and the positively chargeable resin particles have a cationic (positively chargeable) property.

Preparation of negative electrical resin particle dispersion liquid of AOMARKENCODEGTX0AOA

[Preparation] of negatively chargeable resin particle dispersion NA]

A flask containing a thermometer (thermocouple), a nitrogen inlet tube, a stirring device and a condenser (heat exchanger), which had a capacity 2L, was charged with nitrogen, and n-butyl acrylate 250 g and a polymerization initiator (t-butyl peroxy (230 2 - g ethylcaproic acid) tert-butyl peroxide: ARKEKEKEKEKEKEKEY manufactured) 24g were added to the flask. , The internal temperature of the flask was kept unitarily @ (95 °C polymerization temperature), and the contents of the 3 hours flask were stirred into the flask®. Then, a polymerization initiator (t-butyl peroxy (2 - ethylcaproic acid) t-butyl ester: ARKEKEKEKEKEKEKEY Ltd.) 12g, is added to the flask, and the internal temperature of the flask 95 °C is kept unitarily @, and the contents of the flask 3 hours are stirred unitarily.

Next, the contents of the flask 140 °C were dried, and isobutanol was removed under an environment in which the flask type @ and pressure 10 kPa were maintained. Next, the contents of the flask were pulverized to obtain coarse powder fractions. Next, "turbo mill) T250") was manufactured using a mechanical pulverizer (FREREREUND-TURURURURURURURURBOTION), and the above coarse pulverized material was further pulverized under the condition of setting the particle sizes 10 μm to obtain a fine powder crushed material. Next, the resulting fine powder fragment 100 g, cationic surfactant (manufactured "QUUUUARTAMIN (Japan registered trademark) 24P", aqueous sodium lauryl trimethyl ammonium chloride aqueous solution having a concentration 25 mass %) 2g 0.1 hmol/L was mixed, 25g thereby obtaining a dispersion liquid.

Next, ion exchange water, which was added to the resulting dispersion, was added to prepare a slurry of total. 400 g, The obtained slurry was added to a stainless steel pressure-resistant round bottom container. Next, " clearmix (Japan Registered) CLM M M M M (manufactured by M····Ltd.), was used to shear the above-mentioned slurry for 30 minutes under 140 °C the condition that the 2000 0 rpm rotor rotational speed unitunitunitdly @ under the context of a thermostatic unitant type 0.5 mpa and a pressulinic type.), the slurry is chopped. , The contents of the container were stirred 5 °C/under the condition that the temperature of the contents of the container comes 50 °C unitarily @ divided, and the 15000 rpm contents of the container were stirred under the condition that the temperature of the container unitarily @ was found to obtain 30 mass % of the negatively chargeable resin particles (particles made of n-butyl acrylate polymer) containing solid components (negatively charged resin particle dispersion NA). In terms of negatively chargeable resin particles contained in NA of the obtained negatively chargeable resin particle dispersion (NA), the number-50 nm average primary particle 58 °C diameter is unitunitunitant 122 °C, Tg is unitunitunitant @, Tm is unitunitunitant @, and pH 4 4 is - 191900 mV.]On the basis of the data, the negatively chargeable resin particles contained in NA of the negatively chargeable resin particle dispersion have an anionic (negatively chargeable).

[Preparation] of NB with electronegative resin particle dispersion

Into the reaction vessel: bisphenol A propylene oxide adducts (average addition moles of propylene-), bisphenol A ethylene 2 hmol oxide 25 hmol adducts (average number of addition moles of ethylene-oxiranes: unitunitunitaceous @) 2 hmol, 25 hmol fumonings of fumaric 40 hmol acid, and unitz-10 hmol trimellitic anhydride of triacetonicotinyl-trimeltabate®. RTM. Next, in a nitrogen atmosphere, the contents of the container were reacted in the presence of a catalyst (dibutyl tin oxide) to obtain a polyester resin having a number average molecular weight (Mn) 5500, weight average molecular weight (Mw) 11000, Mw / Mn (molecular weight distribution) 2.0, Tg59 °C, Tm122 °C was obtained.

The polyester resin 1300 g obtained as described above was added to a container equipped with a jacketed mixing device (PRIIIMIX Co. Ltd. "T.KKKKKKKKKKKKKKKK.HIVIS-5 type" 120 °C), and the contents of the container were melt-kneaded under the same temperature unit. Next, triethanolamine 100 g, an anionic surfactant of 25 mass % in concentration ("EMAL (registered trade mark) 0", component: sodium lauryl sulfate) aqueous solution 80g was added to the container, and the contents of the 50 rpm container were kneaded for 15 minutes under the condition of the planetary gear rotation speed unitarily @. Then, the ion-98 °C exchanged water 2870 g of the thermostatic type type was added to the container at a 50g /minute rate to obtain an emulsion. , A dispersion (negatively chargeable resin 5 °C/particle dispersion NB) containing negatively charged resin particles (particles 50 °C made of a polyester resin) having a solid content concentration 30 mass % was obtained by cooling the contents of the container until the temperature within the container reaches a unitunitz @ minute period until the temperature within the container reaches the unitunitz @. When the negatively charged resin particles NB contained in the negatively charged resin particle dispersion NB obtained, the number-average primary particle diameter 50 nm is unitunitunitant 59 °C, Tg is unitunitunitant 122 °C, Tm is Kunitunit@, pH 4 4 when pH is - 222mV. Based on the data, the negatively chargeable resin particles contained in the negatively chargeable resin particle dispersion NB have an anionic (negatively chargeable).

Preparation of AOMARKENCODEGTX0AOA by external additive of AOMARKENCODTX0AOA

Preparation] [preparation of external additive EA]

Silica particles (' QSG SG SG-100", negatively chargeable silica particles) 100 g were added to a three-port flask equipped with a thermometer and a stirring device, and the atmosphere in the flask was replaced, with nitrogen gas, and the flask was purged with nitrogen atmosphere. 2LNext, while the contents of the flask were stirred, a surface-treating agent-containing liquid (specifically, 3 - aminopropyl trimethoxysilane 15g was dissolved in a flask-100 ml like liquid) and a proper amount of distilled water was sprayed into the flask, and a proper amount of distilled water was used to promote the reaction (specifically, hydrolysis reaction) on the silica particle surface. Then, the contents of the flask were stirred, and the silica particles were 250 °C reacted with a surface treatment agent (in particular, 3 - aminopropyltrimethoxysilane) 180 minutes under the condition of unit_@ temperature under the condition of unitarity of temperature. Thus, an external additive EA (powder having positively charged silica particles subjected to surface treatment) was obtained (surface-treated powder). In the external additive EA, the number-average primary particle diameter of the positively chargeable silica particles contained in the external additive EA is unitunitunitally 100 nm.

[Preparation] of external additive EB

Titanium dioxide particles (TitananananKogyo, ltd. for "2L KA - 30", negatively chargeable titanium dioxide particles) 100 g, were added to a three-port flask equipped with a thermometer and a stirring device, and nitrogen was replaced, and nitrogen atmosphere. Next, while the contents of the flask were stirred, a surface-treating agent-containing liquid (specifically, 3 - aminopropyl trimethoxysilane 15g was dissolved in Tolulan-like 100 ml liquid) and a proper amount of distilled water was sprayed into the flask, and an appropriate amount of distilled water was used to promote the reaction (specifically, hydrolysis reaction) on the surface of the titanium dioxide particles. Next, the contents of the flask were stirred, and the titanium dioxide particles 250 °C were reacted with a surface treatment agent (in particular, 3 - aminopropyltrimethoxysilane) 180 minutes under the condition of unitarity of the temperature unit_@. Thus, an external additive EB (powder subjected to surface treatment with positively charged titanium dioxide particles) was obtained (powder). In the external additive EB, the number-average primary particle size of the positively chargeable titanium dioxide particles contained in the external additive EB is unitunitunitally 200 nm.

Manufacturing _AOMARKENCODEGTX0AOA of AOMARKENCODTX0AO_toner

Next, a method of manufacturing the toner TA - TA-8 and TB -5 will be described.

[Of Toner TA - 1]

(External additive attaching process)

A FM mixer (NIPIPIPIPX0AO_ENGGGGGGGGINEERING. CO . ltd. "FM - 3500 rpm 10B") was 20 °C mixed 100 g minutes. The core CA of 5 and the external additive EA 3g were mixed under the condition of a tachounitant and a jacket. Thus, the external additive EA (positively charged silica particles) is attached to the localized surface of the core CA. Next, a 300 mesh (Å unitarily 48 μm) screen was used to screen the resulting powder to obtain an external additive attachment nugget CA - 1.

Method (shell layer forming process)

A three-port flask equipped with a thermometer and a capacity 2L of a stirring blade was installed in a water bath. Then, the flask was charged with ion-exchanged Kunitz, 300 ml and the temperature in the flask was 30 °C kept unit_@ using a water bath. Then, hydrochloric acid, was added to the flask, and pH of the contents of the flask was adjusted 4.

Next, 300 g external additives were added to the flask to attach the core CA - 1 and 35g with a positively charged resin particle dispersion PA, and 100 rpm the contents of the flask were stirred 5 mins as unitarily @ rotary speed. Then, the flask contents were stirred, and the 300 ml contents of the 100 rpm flask were allowed to be warmed up to the unitunitz-like 1 °C/speed while the contents of the flask were stirred 65 °C until the flask was added with the ion-exchanged Kunitz @, and the flask contents were allowed to stand under the rated speed unitarily @ minutes. Then, the heating, heating was stopped 65 °C at the flask internal temperature, and cold water was added to 10 °C/the flask to cool the temperature of the contents contained in the flask over a unitz-minute rate. 25 °C. RTM. Next, pH adjustment (neutralization) of the contents of the flask was 7. , A dispersion, in which the external additive EA is not attached in the surface of the external additive attachment core CA - type, is covered with a shell (a layer made of a thermoplastic resin containing a quaternary amine cation group) in the surface of the external additive attachment core CA-1.

(Cleaning process)

, A dispersion of the obtained toner particles was filtered (solid-liquid separation) using a Buchner funnel to obtain a wet cake-shaped toner particle. Next, the obtained wet cake-shaped toner particles were redispersed in ion-exchanged water, and then filtered. , 5 Times of redispersion and filtration, the toner particles were washed.

(Drying process and crushing process)

After that, the washed 35 °C toner particles were allowed to be kept unitarily @ and dried under an atmosphere 48 hours of thermostatic unit_@ and pressure 10 kPa, for example, under an atmosphere of a pressure of equal to or less than a predetermined temperature. Next, a FM mixer (NIPIPIPIPX0AO_ENGGGGGGGGINEERING. CO . ltd. "FM - 10B"), 30 hs the dry toner particles were subjected to a shredding process to obtain positively chargeable toner TA - 1. For toner particles contained in toner TA - 1, the volume median diameter (D) is smaller.₅₀ Kunitz @, 6.0 μm a circularity of 0.965.)In addition, when the surface of the toner particles contained in the toner TA - 1 was observed in the measurement of the coverage of the external additive of>described later, it was confirmed that the external additive EA covers the entire surface of the surface of the core CA that was not covered by the shell layer. , When observing the cross-section of the toner particles contained in the toner TA - 1, a part of the surface of the external additive particles was confirmed to be exposed from the shell layer when the cross section of the toner particles contained in the toner TA-1 was observed in the measurement-AOMARKENCODEGTX0AO_. Further, when the cross section of the toner particles contained in the toner TA - is observed, it is confirmed that the external additive particles protrude from the surface of the shell layer to the radially outer side of the core CA.

[Of Toner TA - 2]

In the shell layer formation step, in addition to the positively chargeable resin particle dispersion PA using 35g instead 35g, the positively chargeable toner TA - 2 is obtained by the same method as in the production of the toner TA - 2. The toner particles included in the toner TA - 2 include a shell layer composed of a thermoplastic resin containing a quaternary amine cation group. Further, in the toner particles contained in the toner TA - 2, the volume median diameter (D) is smaller.₅₀ Kunitz @, 6.1 μm a circularity of 0.964.)In addition, when the surface of the toner particles contained in the toner TA - 2 was observed in the measurement of the coverage of the external additive of>described later, it was confirmed that the external additive EA covers the entire surface of the surface of the core CA that was not covered by the shell layer. , When observing the cross-section of the toner particles contained in the toner TA - 2, a portion of the surface of the external additive particles was confirmed to be exposed from the shell layer when the cross section of the toner particles contained in the toner TA-2 was observed in AOMARKENCODEGTX0AO_, which will be described later. Further, when the cross section of the toner particles contained in the toner TA - 2 is observed, it is confirmed that the external additive particles protrude from the surface of the shell layer to the radially outer side of the core CA.

[Of Toner TA - 3]

In the external additive adhering step, in addition to the external additive EA 10g, the positively chargeable toner TA - 3 is obtained in the same manner as the manufacturing toner TA - 1 except 3g using the external additive EB. The toner particles included in the toner TA - 3 are provided with a shell layer composed of a thermoplastic resin containing a quaternary amine cation group. Further, in the toner particles contained in the toner TA - 3, the volume median diameter (D) is smaller.₅₀ Kunitz @, 6.1 μm a circularity of 0.963.), When observing the surface of the toner particles contained in the toner TA - 3, it was confirmed that the external additive EB is covered by the shell layer in the surface of the core CA when the surface of the toner particles contained in the toner TA-3 was observed in the measurement _AOMARKENCODEGTX0AOA of the coverage rate of the external additive of the TAOMARKENCODEGTX0AO_. , When observing the cross-section of the toner particles contained in the toner TA - 3, a part of the surface of the external additive particles was confirmed to be exposed from the shell layer when the cross section of the toner particles contained in the toner TA-3 was observed in the measurement-AOMARKENCODEGTX0AO_. Further, when the cross section of the toner particles contained in the toner TA - 3 is observed, it is confirmed that the external additive particles protrude from the surface of the shell layer to the radially outer side of the core CA.

[Of Toner TA - 4]

In the shell layer formation step, a 2.0 ml positively chargeable toner TA - 4 was obtained by a method similar to that of the production toner TA - 1 except 35g with an aqueous solution (manufactured "MIRBRBRBANE (registered trademark) Resin SM SM SM SM SM®, manufactured by K.K. K.K. K.K. manufactured by K.K. K.K. K.K. K.K. K.K. ISM-607", solid content concentration 80 mass %) of the negatively-charged resin particle dispersion PA. In the toner TA - 4, the shell layer included in the toner particles is composed of a melamine resin. Further, in the toner particles contained in the toner TA - 4, the volume median diameter (D) is smaller.₅₀ Kunitz @, 6.2 μm a circularity of 0.964.)In addition, when the surface of the toner particles contained in the toner TA - 4 was observed in the measurement of the coverage of the external additive of>described later, it was confirmed that the external additive EA covers the entire surface of the surface of the core CA that was not covered by the shell layer. , When observing the cross-section of the toner particles contained in the toner TA - 4, a part of the surface of the external additive particles was confirmed to be exposed from the shell layer when the cross section of the toner particles contained in the toner TA-4 was observed in AOMARKENCODEGTX0AO_, which will be described later. Further, when the cross section of the toner particles contained in the toner TA - 4 is observed, it is confirmed that the external additive particles protrude from the surface of the shell layer to the radially outer side of the core CA.

[Of Toner TA - 5]

In the shell layer formation step, in addition to changing the amount of the positively chargeable resin particle dispersion PA instead 28g, the positively chargeable toner TA - 5 is obtained in the same manner as in the production of the toner TA - 1. The toner particles included in the toner TA - include a shell layer composed of a thermoplastic resin containing a quaternary amine cation group. Further, in the toner particles contained in the toner TA - 5, the volume median diameter (D) is smaller.₅₀ Kunitz @, 6.1 μm a circularity of 0.960.)In addition, when observing the surface of the toner particles contained in the toner TA - 5, it was confirmed that the external additive EA covers a position not covered by the shell layer in the surface of the core CA when the surface of the toner particles contained in the toner TA-5 is observed in AOMARKENCODEGTX0AO_PO0.AO_. , When observing the cross-section of the toner particles contained in the toner TA - 5, a part of the surface of the external additive particles was confirmed to be exposed from the shell layer when the cross section of the toner particles contained in the toner TA-5 was observed in AOMARKENCODEGTX0AO_, which will be described later. Also, the cross section, in which the toner particles contained in the toner TA - 5 is included, is observed, and it is confirmed that the external additive particles protrude from the surface of the shell layer to the radially outer side of the core CA.

[Of Toner TA - 6]

In the shell layer formation step, the positively chargeable toner TA - is obtained in the same manner as in the production toner TA - 1 except with the aqueous solution (manufactured "MIRBRBRBANE (Japan registered trademark) Resin SM SM SM SM SM-607", manufactured by K.K.). 80 1.7 ml 35gThe toner particles included in the toner TA - are each provided with a shell layer made of a melamine resin. Further, in the toner particles contained in the toner TA - the volume median diameter (D).₅₀ Kunitz @, 6.0 μm a circularity of 0.965.)In addition, when the surface of the toner particles contained in the toner TA - is observed in the measurement of the coverage of the external additive of>described later, it was confirmed that the external additive EA covers the entire surface of the surface of the core CA that was not covered by the shell layer. , When observing the cross-section of the toner particles contained in the toner TA - a part of the surface of the external additive particles was confirmed to be exposed from the shell layer when the cross section of the toner particles contained in the toner TA-6 was observed in AOMARKENCODEGTX0AO_, which will be described later. Further, when the cross section of the toner particles contained in the toner TA - is observed, it is confirmed that the external additive particles protrude from the surface of the shell layer to the radially outer side of the core CA.

[Of Toner TA - 7]

In the shell layer formation step, in addition to changing the amount of the positively chargeable resin particle dispersion PA instead 40g, the positively chargeable toner TA - is obtained in the same manner as in the production of the toner TA - 1. The toner particles included in the toner TA - 7 have a shell layer composed of a thermoplastic resin containing a quaternary amine cation group. Further, in the toner particles contained in the toner TA - 7, the volume median diameter (D) is smaller.₅₀ Kunitz @, 6.0 μm a circularity of 0.965.)In addition, when the surface of the toner particles contained in the toner TA - 7 was observed in the measurement of the coverage of the external additive of>described later, it was confirmed that the external additive EA covers the entire surface of the surface of the core CA that was not covered by the shell layer. , When observing the cross-section of the toner particles contained in the toner TA - a part of the surface of the external additive particles was confirmed to be exposed from the shell layer, as described later in the measurement of the thickness of the AOMARKENCODEGTX0AO_ENCODEGTX0AOA. Further, when the cross section of the toner particles contained in the toner TA - is observed, it is confirmed that the external additive particles protrude from the surface of the shell layer to the radially outer side of the core CA.

[Of Toner TA - 8]

In the shell layer formation step, the positively chargeable toner TA - 8 was obtained in the same manner as in the production of the toner TA - 1 except with an aqueous solution (manufactured "MIRBRBRBANE (registered trademark) Resin SM SM SM SM SM-607", manufactured by K.K.) instead of the positively chargeable resin particle dispersion PA. 80 2.3 ml 35gThe toner particles included in the toner TA - are constituted. Further, in the toner particles contained in the toner TA - 8, the volume median diameter (D) is smaller.₅₀ Kunitz @, 6.2 μm a circularity of 0.950.)In addition, when observing the surface of the toner particles contained in the toner TA - 8, it was confirmed that the external additive EA covers a position not covered by the shell layer in the surface of the core CA when the surface of the toner particles contained in the toner TA-8 is observed in AOMARKENCODEGTX0.AO_. , When observing the cross-section of the toner particles contained in the toner TA - 8, a part of the surface of the external additive particles was confirmed to be exposed from the shell layer when the cross section of the toner particles contained in the toner TA-8 was observed in AOMARKENCODEGTX0AO_, which will be described later. Further, when the cross section of the toner particles contained in the toner TA - is observed, it is confirmed that the external additive particles protrude from the surface of the shell layer to the radially outer side of the core CA.

[Of Toner TB - 1]

In the shell layer formation step, in addition to the negatively charged resin particle dispersion PA using 35g instead 35g of the positively chargeable resin particle dispersion PA, the toner TB - 1. is obtained by the same method as in the production of the toner TA - 1. The toner particles contained in the toner TB - 1 are provided with a shell layer composed of n-butyl acrylate polymers. Further, in the toner particles contained in the toner TB - 1, the volume median diameter (D) is smaller.₅₀ Kunitz @, 6.0 μm a circularity of 0.964.), When observing the cross section of the toner particles contained in the toner TB - 1, it was confirmed that the external additive particles were covered by the shell layer when the cross section of the toner particles contained in the toner TB-1 was observed in the measurement-AOMARKENCODEGTX0AOA of the thickness of the>mentioned later. Thus, in the toner particles contained in the toner TB - 1, the surface of the external additive particle is not exposed from the shell layer.

[Of Toner TB - 2]

In the shell layer formation step, in addition to the negatively charged resin particle dispersion NB using 35g instead 35g of the positively chargeable resin particle dispersion PA, the toner TB - 2. is obtained by the same method as in the production of the toner TA - 1. The toner particles contained in the toner TB - 2 have a shell layer composed of a polyester resin. Further, in the toner particles contained in the toner TB - 2, the volume median diameter (D) is smaller.₅₀ Kunitz @, 6.1 μm a circularity of 0.965.), When observing the cross section of the toner particles contained in the toner TB - 2, it was confirmed that the external additive particles were covered by the shell layer when the cross section of the toner particles contained in the toner TB-2 was observed in the measurement-AOMARKENCODEGTX0AOA of the thickness of the AOMARKENCODEGTX0AO_. Thus, in the toner particles contained in the toner TB - 2, the surface of the external additive particle is not exposed from the shell layer.

[Of Toner TB - 3]

In an external additive adhering step, except that 3g silica particles (' QSG SG SG manufactured by Chemical Industry Co. ", negatively chargeable silica particles) are used instead 3g of the external additive EA, the toner TB - 3 is obtained in the same manner as in the production of the toner TA - 1. The toner particles included in the toner TB - 3 are provided with a shell layer composed of a thermoplastic resin containing a quaternary amine cation group. Further, in the toner particles contained in the toner TB - 3, the volume median diameter (D) is smaller.₅₀ Kunitz @, 6.0 μm a circularity of 0.964.), When observing the cross-section of the toner particles contained in the toner TB - 3, the outer additive particles were confirmed to be covered by the shell layer, as described later in the measurement of the thickness of the AOMARKENCODEGTX0.AO_ENCODEGTX0.AO_ENCODEGTX0.AO_ENCODEGTX0AO_. Thus, in the toner particles contained in the toner TB - 3, the surface of the external additive particle is not exposed from the shell layer.

[Of Toner TB - 4]

In the shell layer formation step, in addition to the positively chargeable resin particle dispersion PA using 35g instead 35g, the toner TB - 4 was obtained by the same method as that of the production of the toner TA - type of the toner composition PC-4. The toner particles included in the toner TB - 4 are provided with a shell layer composed of a thermoplastic resin containing a quaternary amine cation group. Further, in the toner particles contained in the toner TB - 4, the volume median diameter (D) is smaller.₅₀ Kunitz @, 6.0 μm a circularity of 0.964.)In addition, when the surface of the toner particles contained in the toner TB - 4 was observed in measurement-AOMARKENCODEGTX09_, the coverage of the toner particles contained in the toner TB-4 was observed, and the outer additive EA was confirmed to cover the position where the entire surface of the core CA was not covered by the shell layer. , When observing the cross-section of the toner particles contained in the toner TB - 4, a part of the surface of the external additive particles was confirmed to be exposed from the shell layer, when observing the cross-section of the toner particles contained in the toner TB-4 (described later). Further, when the cross section of the toner particles contained in the toner TB - 4 is observed, it is confirmed that the external additive particles protrude from the surface of the shell layer to the radially outer side of the core CA.

[Of Toner TB - 5]

In the shell layer formation step, the 1.4 ml toner TB - 5. was obtained in the same manner as in the production of the toner TA - 1 except that 35g is manufactured by 80 using an aqueous solution (manufactured "MIRBRBRBANE (registered trademark) Resin SM SM SM SM SM-607" manufactured by K.K. K.K. K.K. K.K.). The toner particles included in the toner TB - 5 are constituted. Further, in the toner particles contained in the toner TB - 5, the volume median diameter (D) is smaller.₅₀ Kunitz @, 6.1 μm a circularity of 0.965.)In addition, when observing the surface of the toner particles contained in the toner TB - 5, it was confirmed that the external additive EA covers a position not covered by the shell layer in the surface of the core CA when the surface of the toner particles contained in the toner TB is observed in the measurement>of the coverage rate of the external additive. , When observing the cross-section of the toner particles contained in the toner TB - 5, a part of the surface of the external additive particle was confirmed to be exposed from the shell layer, when observing the cross-section of the toner particles contained in the toner TB-5, as described later, was observed. Further, when the cross section of the toner particles contained in the toner TB - 5 is observed, it is confirmed that the external additive particles protrude outside the core CA from the surface of the shell layer.

Measurement of thickness of AOMARKENCODTX0AO_shell layer, AOMARKENCODEGTX0AOA

The toner as a measurement object was dispersed in an epoxy resin curable at room temperature, 40 °C and allowed to cure 2 days under an atmosphere of a room temperature unit_@. The resulting cured product was dyed with osmium tetroxide. Through this process, only the shell layers in the toner particles are selectively dyed. Next, an ultra-thin slicer equipped with a diamond cutter ("EM UC6" manufactured by Leica ica ica Co. Ltd.), and a dyed cured product were cut out, and a sheet sample. Next, a cross section of the obtained sheet sample was photographed by a transmission electron microscope (TEM) ("H-7100 FA" manufactured by Hitititachi High-Technologies logies '), with 10-fold magnification. Then, TEM images were analyzed, using image analysis software (manufactured by manufactured "WinininROOF"), to measure the thickness. In particular, two straight lines perpendicular to the approximate center of the cross section of the toner particles, respectively, are drawn in 2 positions where the 4 straight lines and the shell layers intersect, respectively, to measure the thickness. An arithmetic mean of the thickness of 4 positions measured is taken as the thickness. 10 Of the toner particles contained in the toner as the measurement target respectively measure the thickness, the average value of the measured thicknesses, and the evaluation value (thickness).

Measurements of coverage of AOMARKENCODEGTX0AO_INDOMAKENCODEGTX0AOA

The toner as a 25 °C measurement object was exposed 5 minutes. C. in steam at a concentration 20 mass % of a ruthenium aqueous ruthenium peroxide 2 ml solution under an atmosphere of a room temperature unit_@. Thus, the toner was subjected to ruthenium staining. This step, in the surface of the toner particles contained in the toner, only the shell layer is selectively dyed, and the external additive particles are not dyed.

Next, the stained toner was photographed by a field emission scanning electron microscope (FE-SEM) (' JSM-76600 F " manufactured by JEOL Ltd.), and a back-scattered electron image (surface-captured image) of the toner particles was obtained. In the surface area of the toner particles, the area (staining area) stained with ruthenium is displayed brighter than the area (non-staining area) not stained with ruthenium. In addition, the image capturing conditions of the back-scattered electron image of the toner 10.0 kv particles are the following: the accelerating voltage unitunitunits, the irradiation current 95 μA, the magnification 250000 times, the contrast 4800, and brightness (brightness) 550. FIGS.

Next, image analysis of the back-scattered electron image using image analysis software (manufacturing "WinininROOF") was carried out using an image analysis software (manufactured by three-grain commercial). In particular, the surface region (rectangular region in the longitudinal 2 µm ×) of the center of the toner particles 2 μm in the back-scattered electron image is cut out, and a Gaussian filter process 5 ×5 of the resulting image data is performed. In addition, the surface area in the vicinity of the center of the toner particles is a rectangular region of the back scattering electron image, and the longitudinal 2 µm × cross unit_type 2 μm is depicted as a base point (centroid) of the toner particles. Then, image data (area: 2 µm ×2 µm; number of pixels: 1280 ×1024) subjected to filter processing [vertical axis: frequency (number) of pixels); horizontal axis: luminance] are obtained. The brightness value histogram shows distribution of the brightness values of the surface area (staining area and non-staining area) of the toner particles.

As for the luminance value histogram obtained as described above, Solver, which is manufactured "MICCCCCCCEL (registered trademark)") using a table calculation software ('MICROSOFT EXCEL (Japan registered trademark)') is used to perform fitting and waveform separation of normal distribution by the least-squares method. As a result, the non-staining waveform representing the distribution (normal distribution) of the luminance values of the non-staining area and the distribution (normal distribution) of the luminance values of the staining area (normal distribution on the high brightness side) are obtained. Then, based on the area (RC: area; RS: area) of the obtained 2 waveforms, the coverage (unit: %) of the external additive was determined based on the following equation, depending on the area (RC: area of the non-stained waveform; RS: area of the stained waveform). Also, it is considered, in the above image data, that a pixel belonging to a non-staining waveform represents an external additive particle. Further, it is considered, in the above image data, that a pixel belonging to a staining waveform represents a shell layer. Thus, by the following equation, the area ratio (coverage rate). of the area covered by the external additive in the surface area of the toner particles can be determined.

External additive coverage=100×RC/ (RC+RS)

Table specifically indicates cores, shell layers and external additives of the toners TA - TA-8 and TB -5, respectively. 1Table 1, "PA-QA" means a thermoplastic resin containing quaternary amine cation groups in the positively chargeable resin particle dispersion PA used in the shell layer formation step (PA-QA). "PB-QA" means a thermoplastic resin containing a quaternary amine cation group in the positively chargeable resin particle dispersion PB used in the shell layer forming step, for. "PC-QA" means a thermoplastic resin containing a quaternary amine cation group in PC of a positively chargeable resin particle, which is used in the shell layer forming process. 'PC-QA' means a thermoplastic resin. "MR" represents a melamine resin. "BA" denotes a n-butyl acrylate polymer. "PES" means a polyester resin. "P-Si" means positively charged silica particles. "P-Ti" means positively charged titanium dioxide particles. "N-Si" means negatively charged silica particles. In addition, "-" in the softening point of the resin of the shell layer indicates that there is no measurement of the softening point. Further, in a column of the coverage of the external additive, "-" means that the coverage of the external additive is not measured.

[Table 1]

AOMARKENCODEGTX0AO_assessing Method _AOMARKENCODEGTX0AOA

Preparation] [preparation of two-component developer]

Each raw material (MnO, MgO, Fe)₂ O₃ Each raw material) SrO is suitably blended, so MnO can be converted into a unitunitic @, MgO-based and Fe 39.7 hmol %-based Mn- and Fe 9.9 hmol %-based alloy.₂ O₃ SrO is unitarily 49.6 hmol %, SrO is unitarily 0.8 hmol %, and the blended raw materials are added with water. This is followed 10 hours, when used, is crushed and mixed. , The resulting mixture was dried. Then, the dried mixture was unitunitedly @ heat treated under the 4 hours presence 950 °C of a constant temperature unit_type of temperature.

Next, the above-described heat-24 hours treated mixture was pulverized using a wet ball mill, and the resulting mixture was pulverized to prepare a slurry. Next, the obtained slurry was dried and pelletized by a spray dryer. Then, the dried granules were kept unitarily @ in an atmosphere of a 1270 °C unitz-type 2% and an oxygen-concentration unitz 6 hours-type, and then pulverized. Then, by performing particle size adjustment, a powder (number-average primary particle particle shape @) Mn-Mg-Sr ferrite particles (magnetic 35 μm carrier core), and the Mn-Mg-Sr ferrite particles were obtained at 3000 (10).³ Saturated magnetization under applied magnetic field/4 π · A/m 70A ·m)² . Ltoreq/kg.

Next, a polyamideimide resin (a copolymer of trimellitic anhydride and 4, 4' - diaminobenzophenylmethane) was diluted, and a resin solution having a solid content concentration 10 mass % was prepared by diluting the polyamideimide resin (copolymer of trimellitic anhydride) with methyl ethyl ketone. , FEP (tetrafluoroethylene - hexafluoropropylene copolymer) was dispersed in the resulting resin solution, and silicon oxide, in a proportion 2 mass % with respect to the total resin content, was added to obtain a washcoat liquid having a solid content of 150 g in terms of solid content. The mass ratio (polyamide-imide resin: FEP) of the polyamide-imide resin to FEP is @timetime@ in the case of the obtained carrier-overcoat liquid 2:8.

Next, "SPIIIIRA COTA (Japan Registered) SP - 25"), which was obtained in the above-described procedure was coated with the washcoat liquid using a rotary drum fluidized bed coater (Ookra Co. Ltd. Ltd.), and the magnetic carrier core (Mn-Mg-Sr ferrite 10 kg particles) was unitarily @. Then, the coated 220 °C magnetic carrier core of the resin coated with the resin unitarily @ unitarily 1 hour unitarily and is calcined. Thus, an evaluation carrier was obtained. The resin coating amount of the carrier for evaluation was 1.5 mass % with respect to the entire carrier.

Using a ball mill, the two-component developer was obtained by mixing parts by mass of the carrier and sample (toner for evaluation) of parts by mass, as described above. 10 30 100

[Low-temperature fixability (minimum fixing temperature) evaluation]

The evaluation device uses a color multi-function all-in-one machine with a fixing device (which manufactures "TASASASASASASASAS550CI") to an evaluation device that can change the fixing temperature.). The surface of the heating roller of the fixing device is PFA (tetrafluoroethylene - perfluoroalkyl vinyl ether copolymer) hose 5 μm having a thickness 30 μm ± 10 µm, a surface roughness (Ra: arithmetic average roughness) unitunitunitan @ type. The two-component developer prepared in the above step is added to the cyan developing device of the evaluation apparatus, and the toner for evaluation is added to the cyan toner container of the evaluation apparatus.

Using the evaluation apparatus described above, the unit weight 25 °C 90g/m is set in an environment in which the thermostat units @ and the humidity 50% RH.² On paper (printed paper of A4 size), unitz @ sec (300 mm/paper orientation: transverse conveyance), toner application, and unitunitunit_@ second (paper orientation: transverse conveyance) are applied 0.4 mg/cm.² Conditions, a solid image of a size 25mm×25mm (in particular, an unfixed toner image) is formed. Then, the sheet forming the image is passed through the fixing device of the evaluation apparatus. At this time, it is determined whether or not the 80 °C fixing temperature (toner 5 °C image) of the solid image (toner image) can be fixed to the lowest temperature (the lowest fixing temperature) of the sheet at each fixing temperature while the fixing temperature of the fixing device is set to unitarily. The toner fixing, which was confirmed. In particular, the sheet passing through the fixing device is inside, and is folded into half, with the center of the image as half, and 5 back and forth 1 kg are rubbed on the crease by using a weight made of brass-clad brass, at the center of the image. Then, the sheet, a bending portion (a portion in which a solid image is formed) of the sheet is observed. Then, the length (peeling length) of the toner peeling off the bent portion was measured. The lowest temperature at which the peeling length 1 mm of the fixing temperature falls below 'unit_@' is used as the lowest fixing temperature. The results are shown 2. Below the lowest fixing temperature 100 °C, the lowest fixing temperature was evaluated to "be particularly good", and the 100 °C lowest fixing 105 °C temperature was found to be 'unitless @' and the lowest fixing temperature was found to "good". The low-temperature fixability was evaluated to be 'good'. Further, in the case where the 105 °C lowest fixing temperature is exceeded unit_@, the low-temperature fixability was evaluated to "not good".

[Of heat-resistant storage property (agglutination rate)]

3g Toner (Toner for evaluation) was charged into a polyethylene container and the polyethylene container was 20 ml sealed.], a polyethylene container was sealed. After 5 minutes of the sealed container was subjected to a beating treatment, the container was statically placed in a thermostatic bath unitz 8 hours-type which was 60 °C set to a unitunit_@ type. Then, the toner taken out from the container was cooled to room temperature (25 °C) to obtain an evaluation subject.

Obtained evaluation objects are placed on a mass-known 300 mesh (pore-like) screen mesh. The present invention is not 48 μm limited to these examples. , The mass, including the evaluation subject, of the screen was measured, and the quality. Next, the screen was mounted to a powder characteristic evaluation device (manufactured by Jichuan Co. "Powder der der Tester (registered trademark) PT-X"), and the screen was screened unitarily with the use manual 1.0 mm, such as a powder characteristic 30 hs evaluation device, to screen the evaluation object. 'unitz @, ' unitz ' was used. After screening, the quality of the toner without passing through the screen was measured. , The aggregation rate (unit: mass %) was determined according to the following equation based on the mass of the toner before the screening and the quality, based on the quality of the toner after screening. The results are shown 2. The flocculation rate was 10 mass % or less, and "good" thermal storage property was evaluated. Further, when the aggregation rate exceeds 10 mass %, the heat-resistant storage property is evaluated to "be bad". In addition, "in the following formula ' the quality" of the toner after screening is the quality of the toner which does not pass through the screen, and is the quality.

Quality/quality of toner before mass/screening of toner after coagulation factor=100 100

[Anti-thermal stress resistance (temperature) of 5 mN·m hours]]. [!

The evaluation device uses a rheometer (Anton manufactured "MCR R R R-301"). Shows the outline rheometer rheometer) of the present invention. 3, With reference to FIG. 3, an evaluation method of thermal stress resistance will be described.

As shown 3 shows, the evaluation apparatus 30 includes a press head 31 made of aluminum, a flat plate 32 made of stainless steel (SUS), and a heating device 33. The pressure head 31 has a shape that the area of the bottom surface F20 falls unitarily. 0.785 cm² Cylindrical. The platen 32 is fixed, and the ram 31 is driven by the motor to move. The head 31 is displaced in a direction (Z1 direction or Z2 direction) orthogonal to the top surface of the plate 32 so that the distance between the bottom surface F20 of the indenter 31 and the top surface of the plate 32 is changed. The toner particles 34 (toner particles contained in the toner for evaluation) are sandwiched between the bottom surface F20 of the press head 31 and the top surface of the plate 32, and a predetermined pressure can be applied to the toner particles 31 by moving the head 32 toward the plate 34 (displacement toward Z2 side), for example. Further, the pressure head 31 is driven by the motor to rotate about the rotation shaft in a direction orthogonal to the top surface of the flat plate 32, for.

In the evaluation of thermal stress resistance, the head 31 is rotated at 1 Hz frequency per rotation yaw angle 0.01 ° so that the press 1.0 mg head 31 applies a certain pressing load to toner particles 34 unitarily @ thereto (3.0N/cm).² In, the temperature of 2 °C/the toner particles 34 is raised as unitz @ minute, and the rotation torque of the pressure head 31 is measured at 5 mN·m temperature.)When the toner particles start to dissolve, the rotational torque rises 5 mN·m or more, and when the toner particles dissolve to a certain extent, the rotational moment tends. If the rotation torque was 5 mN·m ° C. 58 °C or more, the thermal stress resistance was evaluated to "good" 58 °C, and the temperature was found to be 'good' and the thermal stress resistance was evaluated as "bad". the thermal stress resistance was evaluated. The results are shown 2.

[Table 2]

Among the toners TA -8, the external additive is attached to the surface of the core of the toner particle without being covered by the shell layer. In the toner TA -8, a portion of the surface of the external additive particle is exposed from the shell layer. In the toner TA -8, the external additive particles protrude more radially outward. As shown, the toner TA - TA-8, the shell layer contains a thermoplastic resin (thermoplastic resin) having a softening point higher than that of the core or a thermosetting resin. 1 2ndIn the toner TA - TA-8, the thickness of the shell layer exceeds unit_% or more. 5 nm

As shown, the toner TA - TA-8, the flocculation rate is mass % or less. 2 10Thus, the heat resistance of the toner TA - TA-8 is good. Toner TA - type, the temperature at which the rotational torque is may be unitunitless or more. 5 mN·m 58 °CThus, the thermal stress resistance of the toner TA - TA-8 is good.

In Toner TB - 3, the surface of the external additive particle is not exposed from the shell layer. As shown 1, in the toner TB - 4, the resin constituting the shell layer is a thermoplastic resin having a softening point lower than the softening point of the core. In the Toner TB - 5, the thickness 5 nm of the shell layer is substantially similar thereto.

As shown, in the toner TB - 4, the aggregation rate exceeds mass %. 2 10Thus, the heat resistance of the toner TB - 4 to TB-4 is poor. In Toner TB - 5, the temperature at which the torque is is less than the unitunit_type. 5 mN·m 58 °CAs a result, the thermal stress resistance of the toner TB - 5 to TB-5 is poor.

The above results show that the toner according to the present invention can improve heat resistance and thermal stress resistance.